Perfume compositions containing hexahydro-1,4,9,9-tetramethyl-4,7-methanoazulenones

ABSTRACT

NOVEL HEXAHYDRO-1,4,9,9-TETRAMETHYL-4,7-METHANOAZULENONES USEFUL AS OLFACTROY AGENTS; PERFUME COMPOSITIONS CONTAINING SUCH AZULENONES; AND METHODS FOR PREPARING SUCH AZULENONES AND SUCH COMPOSITIONS.

United States Patent Office 3,8 14,7 04 Patented June 4, 1974 U.S. Cl. 252-522 2 Claims ABSTRACT OF THE DISCLOSURE Novel hexahydro 1,4,9,9 tetramethyl-4,7-mcthanoazulenones useful as olfactory agents; perfume compositions containing such azulenones; and methods for preparing such azulenones and such compositions.

This application is a division of United States application Ser. No. 735,545, filed June 10, 1968, now US. Pat. 3,679,750.

BACKGROUND OF THE INVENTION Materials which can provide amber and woody fragrance notes are known in the art of perfumery. Many of the natural materials which provide such fragrances and contribute desired nuances to perfume compositions are high in cost and generally subject to the vagaries of natural products such as variability in crop quality.

There is accordingly a continuing effort to find synthetic materials to replace these natural materials for fragrance notes in perfume compositions, but many of these synthetic materials either have the desired nuance only in relatively small amounts or else contribute undesirable or unwanted fragrances to compositions. For example, Buchi et al., 84 J.A.C.S. 3205 (1962), show the production of hexahydro-4,9,9-trimethyl-A -4,7-methanoazulene-1(2'I-I)-one. The odor of this ketone was not stated. It is found to have a weak woody odor.

THE INVENTION rated lretones having the structure R1 ll wherein one of R and R is oxygen and the other represents two hydrogen atoms, R is methyl, or when R is oxygen, methyl or methylene, and one of the dashed lines represents a double bond. It also relates to the use of these unsaturated ketones as olfactory agents and in perfume compositions, as well as in the preparation of such compositions. The novel azulenones of the present invention provide a superior intense, camphoraceous woody amber fragrance note. Accordingly, smaller quantities can be used to impart a camphoraeeous, woody amber fragrance to perfume compositions and to perfumed articles, such as soap, face powder and other articles as disclosed hereinafter.

The novel materials according to the present invention can be considered as hexahydro derivatives of methanoazulene and are hexahydro-1,4,9,9 tetramethyl-A -4,7- methanozulen-3 (2H)-one hexahydro-1,4,9,9-tetramethyl A -4,7-methanoazulen- 3(2H)-one O fin hexahydro 1 methylene 4,9,9 trimethyl-A -4J- methanoazulen-3 (2H) -one 0 i (In) hexahydro l,4,9,9 tetramethyl M 4,7 methanoazulen-8 (7H) -one and mixtures thereof. It will be appreciated that the foregoing structures include the various stereoisomeric forms.

The unsaturated ketones can be used individually or in admixture. Generally, the ketones are utilized in admixture, and in many aspects of the present invention a mixture of the four cyclic ketones is preferred.

The unsaturated ketones of this invention are useful as olfactory agents and fragrances. They have a camphoraceous woody amber fragrance in their own right and can impart this fragrance note to perfume compositions and perfumed articles according to the present invention. They can either be formulated into, or used as components of, perfume compositions.

The term perfume composition is used herein to mean a mixture of organic compounds, including, for example, alcohols, aldehydes, ketones, esters and frequently hydrocarbons which are proportioned so that the combined odors of the individual components produce a pleasant or desired fragrance. Such perfume compositions usually contain: (a) the main note or the bouquet" or foundation-stone of the composition; (b) modifiers which round-off and accompany the main note; (0) fixatives which include odorous substances which lend a particular note to the perfume throughout all stages of evaporation, and substances which retard evaporation; and ('d) topnotes which are usually low-boiling fresh-smelling materials.

In perfume compositions the individual component will contribute its particular olfactory characteristics, but the overall effect of the perfume composition will be the sum of the effects of all ingredients. Thus, the individual compounds of this invention, or mixtures thereof can be used to alter the aroma characteristics of a perfume composition, for example, by highlighting or moderating the olfactory reaction contributed by other ingredients in the composition.

The amount of mixtures or compounds of this invention which will be effective in perfume compositions depends on many factors, including the other ingredients, their amounts and the effects which are desired. It has been found that perfume compositions containing as little as 2% by weight of mixtures or compounds of this invention, or even less, may be used to impart a fine woody amber odor to soaps, cosmetics and other products. The amount employed can range up to 5-7% or higher and will depend on considerations of cost, nature of the end product, the effect desired on the finished product and the particular fragrance sought.

The azulene ketones described herein can be used alone or in a perfume composition as olfactory components in detergents and soaps; space deodorants; perfumes; colognes; bath preparations such as bath oil, bath salts; hair preparations such as lacquers, brilliantines, pomades, and shampoos; cosmetic preparations such as creams, deodorants, hand lotions, sun screens; powders such as tales, dusting powders, face powder; and the like. When used as an olfactory component of a perfumed article, as little as 0.01% of the novel ketones will suffiee to impart an amber, camphoraceous woody odor. Generally it is preferred not to use more than 0.5% because no additional benefit is obtained and the fragrance may become unbalanced.

In addition, the perfume composition can contain a vehicle or carrier for the other ingredients. The vehicle can be an absorbent or adsorbent solid such as a gum or components for encapsulating the composition.

The novel unsaturated ketones of this invention are prepared by oxidizing 1,4,9,9-tetramethyl-A -octahydro-4,7-methanoazulene commonly called beta-patchoulene, to provide unsaturated ketones having the structure in acid medium to form a methano bridge by cyclization and dehydration. Bulnesol is conveniently obtained from g'uaiacwood oil. The cyclization is carried out by treating the bulnesol or bulnesol fraction of guaiacwood oil with p-toluene sulfonic acid and formic acid in a vehicle such as toluene. The mixture is heated at reflux till the evolution of water ceases. The reaction mixture is then neu- 4 tralized with an alkali such as an alkali-metal hydroxide like sodium hydroxide and distilled to obtain the betapatchoulene.

The oxidation reaction of this invention is carried out by treating the patchoulene with an agent which will oxidize a methylene group in the position alpha to a carbon-carbon double bond. Suitable agents are metal oxides such as chromium trioxide, selenium dioxide, and the like and alkali-metal dichromates such as sodium dichromate, potassium dichromate, and the like. It will be understood by those skilled in the art that materials furnishing these oxidizing agents under the reaction conditions can be used in the practice of this process.

It is frequently desirable to carry out the reaction in an acidic milieu, and acids suitable for this purpose include both strong mineral acids such as sulfuric acid and the like and organic acids such as acetic acid, acetic anhydride, and other lower alkanoic acids and their anhydrides. Thus, the combination of sulfuric acid with alkalimetal dichromates and of acetic acid and/or acetic anhydride with chromium trioxide is used. Chromium trioxide-acetic acid is the preferred oxidizing agent because of its specificity in oxidizing a methylene to a carbonyl.

The time and temperature at which the reaction is carried out are interrelated. It has been found that temperatures of from about 10 C. to about C. can be used in carrying out the process of the present invention. The reaction time is chosen to obtain the desired yields of the unsaturated ketones. Thus, it has been found that the reaction can be carried out for 15 to 20 days at 20- 30 C. or for 20 to 22 hours at 5060 C. with good results.

The reaction is preferably carried out in an inert vehicle which will not be attacked by the reactants under the reaction conditions and which will serve to promote contact between the reactants and to moderate the reaction. The vehicle can be a solvent for reactants. It is preferred to have t-butanol present.

The amount of oxidizing agent can be varied over a range depending upon the desired reaction rate, the particular oxidizing agent, the reaction vehicle employed, and the time and temperature of the reaction. It is generally preferred that an equimolar or greater quantity of oxidizing agent, based on the amount of patchoulene, be present. The quantity of acid present should be from 10 to 20 equivalents, based on the beta-patchoulene.

The reaction can be carried out over a wide range of pressure from subto superatmospheric. It is generally preferred to carry out the reaction under atmospheric pressure.

Depending upon the particular isomer or isomer mixture of ketones prepared according to this invention the ketones can be purified and/or isolated as desired. Any unreacted chromie oxidizing agent can be decomposed with a suitable agent, such as oxalic acid. The final unsaturated ketone is desirably purified to remove unreacted materials, by-products, color bodies, foreign odor bodies, and the like. The purification and/or isolation of the products can be carried out by conventional techniques. Thus, the products can be purified, separated, and/or isolated by distillation, extraction, preparative chromatographic techniques, and the like. It is frequently desirable to wash and dry the mixture of ketones prior to final purification and/ or isolation.

As disclosed above, the novel unsaturated methanoazulene ketones of this invention can be utilized as olfactory agents and in perfume and perfumed articles. They can also be further treated to obtain other useful materials. Thus, copending application Ser. No. 735,544, now US. Pat. 3,679,749 filed in the name of James D. Grossman et al., entitled Novel Process and Products, discloses methods for the production of perhydro alcohols from the novel unsaturated ketones of this invention. Such alcohols can be further treated to provide saturated ketones having great utility as olfactory agents.

All parts, proportions, percentages, and ratios herein are by weight, unless otherwise stated.

The following Examples are given to illustrate embodiments of the invention as it is presently preferred to practice it. It will be understood that these Examples are illustrative and the invention is not to be considered as restricted thereto except as indicated in the appended claims.

EXAMPLE I Direct oxidation of beta-patchoulene to form unsaturated ketones A. Oxidizing agent.Into a three-liter reaction flask equipped with a reflux condenser, Y-tube, stirrer and ni trogen purge means, 1.2 liters of t-butyl alcohol is introduced. During nitrogen purging, 400 g. of anhydrous chromium trioxide is added to the t-butyl alcohol over a one-hour period. The reaction mass is then dissolved in Mass spectra of the four materials show peaks (in order of decreasing intensity) on a Consolidated Electrodynamics Corp. Model 21-103C instrument:

Parent peaks Other peaks carbon tetrachloride (2 liters) and washed with three 500 NMR bands Interpretation cc. portions of water and dried over anhydrous sodium 150mm. (8) ouormula I: sulfate.

B. Direct oxidation reaction.lnto a 12- liter reaction 0 'gzf fa g ifif GHPCLFCH' flask equipped with a reflux condenser, stirrer, Y-tube, (6H). thermometer and addition funnel, are placed: Douglas at H Beta-patchoulene g 200 25 Hi Cr( J-c=c Carbon tetrachloride liters 2 l Acetic anhydride c 160 Slnzletat 76 Hz. 1 Acetic acid ee 600 H 2-3 The mass is stirred and heated to 50 C.

A solution is obtained by admixing 3 /2 liters of the [Facing/0:0] chromium oxide/t-butyl alcohol complex prepared as in A above, 160 cc. of acetic anhydride, and 600 cc. of isomer (b) 0 orm a acetic acid. This solution is added dropwise to the beta- 0 Two single, at patchoulene solution over a 2% hour period, while main- 35 50 and 55 Hz. ogi-cc l i taining the reaction mass at 50 C. The reaction mass is I then stirred for 20 hours at 5 0 C. Doublets at 63 H The reaction mixture is then washed with a solution of f' gf 1500 g. of oxalic acid in 12 liters of water, twice with l l 500 cc. of water, neutralized with saturated Na- CO solusinglet 8,11% H tion and then again twice with water. The 'washed mate- H (3 1 rial is dried over anhydrous sodium sulfate and concentrated under vacuum.

The crude concentrated material (195 g.) is distilled at 113l48 C. and 1.8-0.8 mm. Hg to yield a mixture of I, II, III, and IV. This mixture has a pleasant woody- Compound u amber camphoraceous patchouli-like odor. The individual T Si 1 t t compounds are separated by gas-liquid chromatography 0 W 58 (GLC) (20 x A column containing 5% Carbowax 2123 9 20M polyethylene glycol coated on Anakrom ABS Si M t 68H I silanized acid-washed calcined diatomaceous earth made by Analab, Inc., Hamden, Conn.; flow rate, 100 microl liters/minute; column temperature, 220' C.; chart speed,

I has a strong patchouli camphor aroma.

H has an excellent minty-camphory-woody odor, and a gg at CH I patchouli note as well as a peppery fragrance note. II is obtained by means of fractional distillation. Isomer(a) otlormula III:

' II has an ambery-cedar woody aroma and a desirable Two singlets at l incense quality. 51 and 54 Hz. CHr-C-CHI IV has a woody-camphory odor. (6E1)- l According to GLC analysis, the ratio of I:IH:IV is ap- I Doublets at 53 H proximately 17.7% :65.0% 17.2% and 64 Infrared analysis of the four materials yields the fol H l lowing data: I 65 Table I shows the absorption bands (in cmr' of varisinglet at cg,-r c=c ous structural features of the four compounds. I

TABLE I Compound I II III IV 5-memberedrlngcarbony1 1,625.1,695 (coniugated).-- 1,740(non-con1ugated) None 1,700 (conjugated) Methylene alphato carbonyl i 1, dn Gem-dimethylaudlorZmethyIgroup 1,370- (2Megroups) 1,870-90(2Megroups) 1,370-00(2Megr0ups). 1,390 (1 Me group)- a-membered conjugatedring ketooo N N 1,625, ,670 None. Conjugated C=C hoods do do do 1,570, 1,630. Exo-vinylidenelu5-memberedrinz do do do 885.3,080.

7 TABLE-Continued NMR bands Interpretation Isomer (b) of formula III:

Singlet at 54 Hz. I (6H). CEr- Cf-CE: I Singlet at 65 Hz. I c g.-c-o=on on, I

O Doublet at 63 H and 70 Hz. I

C 1 r(|J-C=C- Compound IV:

Two singlets at I 50 and 55 Hz. CHr-G-CE: l I Singlet at 78 Hz. C r-C-C=C 1 (3H).

[Facing C=O1 Broad singlet at 0 170 Hz. (2H).

7 C=GCr-C- Broad doublet at 0:0 H:

298 Hz. (2H).

The presence of conjugated carbonyl in compounds I and IV is indicated by A at 274 and 242 m respectively, in the ultraviolet spectra.

EXAMPLE 'H The ketone mixture prepared in Example I is dissolved in alcohol to obtain a 10% solution, and a second 10% solution is prepared by dissolving hexahydro-4,9,9-trimethyl-A -4,7-methanoazulen-1(2H)-one (the trialkyl azulene material produced by Buchi et al., supra, hereinafter called the trialkyl azulene material) in alcohol. A 10% solution of ketones prepared according to Example I has a strong camphoraceous woody amber fragrance, whereas the other solution is almost odorless. A 1% solution of the ketones prepared in Example 1 displays a distinct, recognizable patchouli-like odor and is still considerably stronger than the 10% solution of the trialkyl azulene material.

Similar results are obtained with the individual ketones I, II, III and IV prepared according to the present invention.

EXAMPIJE III Perfume composition A further comparison is carried out utilizing the following perfume base compositions:

To separate samples of the foregoing base are added (A) five parts of the trialkyl azulene material, (B) five Amount (parts) 8 parts of the ketone mixture of Example I, and (C) five parts of patchouli oil.

Sample A shows substantially no change in aroma from the base composition, while sample B shows the woody, oriental fragrance effect resembling that obtained by the use of genuine patchouli oil (Sample C).

EXAMPLE IV Perfume composition A perfume composition is prepared with the following ingredients:

The perfume composition exhibits an excellent woody fragrance. When the ketone mixture is omitted, the composition lacks the woody, amber fullness of the complete perfume composition of this Example.

It will be understood from the present description that the individual ketones of the present invention can be used separately or in combination with each other to provide a good intense camphoraceous woody frangrance note.

In the following Examples, the soap base and soap chips used are unperfumed sodium-based toilet soaps made from tallow and coconut oil. The detergent powder is a material obtained from Lever Bros. Co. and sold under the trademark Rinso." The liquid detergent is a product manufactured by Ultra Chemical 00., and is known as P-87 liquid detergent.

EXAMPLE V Preparation of soap composition One hundred grams of soap chips are mixed with one gram of the perfume composition of Example IV until a substantially homogeneous composition is obtained. The perfumed soap composition manifests an excellent woody, amber, patchouli odor character.

EXAMPLE VI Preparation of a detergent composition A total of 100 grams of detergent powder is mixed With, 0.15 grams of the perfume composition of Example IV until a substantially homogenons composition is obtaned. ThlS composition has an excellent woody, amber 0 or.

EXAMPLE VII Preparation of a cosmetic powder composition A cosmetic powder is prepared by mixing in a ball mill 100 grams of talcum powder with 0.25 grams of the mixture obtained from the process of Example I. The powder has an excellent camphoraceous, woody, patchouli-like odor.

EXAMPLE VIII Perfumed liquid detergent Concentrated liquid detergents with a camphoraceous woody, patchouli-like odor are prepared containing 0.10%, 0.15%, and 0.20% of the 3-one of this invention. They are prepared by adding and homogeneously mixing detergent. The detergents all possess a camphoraceous having the structure I g ----I wherein one of R or R is oxygen and the other represents two hydrogen atoms, R is methyl or when R is oxygen, R is methyl or methylene, and one of the dashed lines represents a double bond and a vehicle or carrier.

2. A perfumed article comprising soap, detergent, space deodorant, creams, lotions or talc and a fragrance effective amount of a 'ketone having the formula wherein one of R or R, is oxygen and the other represents two hydrogen atoms, R, is methyl, or, when R is oxygen, R is methyl or methylene, and one of the dash lines represents a double bond.

References Cited Brown et al., Chem. Abst., Vol. 66 (1967), p. 64847b.

SAM ROSEN, Primary Examiner UNITED STATES PATENT OFFICE F 2o28B- A CERTIFICATE OF CORRECTION Patent No. 3 814 704 I D d June 4 1974 l BRAJA D.' MOOKHERJEE It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 2, line 8, correct the spelling of "methanogzulen-3" Col. 5, line 59, "II" should read -III-- I Col. 6, line 40, in the tabulation under "NMR bands",

"Singlet at Hz" should read Singlet at 22 Hz-.

Col. 9, line 15, in claim 1, "or" should read -and-- Col. 10, line 11, claim 2, "or" should read -and-.

Signed and sealed this 21st day of January 1975.

(SEAL) Attest:

s N JR. 0. MARSHALL DANN i rii gt ng f cer Commissioner of Patents ORM P040550 uscoMM-oc 60376-P69 U 5 GOVEINMFNT PRINTING OFFICE 1!, 0366434 

